Sodium Carbonate → HCID 22613898, compound

HRID 844615Notes

Reaction equation

HRID 844615 reaction equation
C(=O)([O-])[O-].[Na+].[Na+].C(C1C=C(B(O)O)C=CC=1)#N.[C:18]([C:20]1[CH:21]=[C:22]([C:26]2[CH:31]=[C:30]([CH3:32])[CH:29]=[C:28]([O:33][CH2:34][C:35]([O:37][CH3:38])=[O:36])[CH:27]=2)[CH:23]=[CH:24][CH:25]=1)#[N:19].C1C(=O)N([Br:46])C(=O)C1>C1(C)C=CC=CC=1.CO.C(Cl)(Cl)(Cl)Cl.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[C:18]([C:20]1[CH:21]=[C:22]([C:26]2[CH:31]=[C:30]([CH2:32][Br:46])[CH:29]=[C:28]([O:33][CH2:34][C:35]([O:37][CH3:38])=[O:36])[CH:27]=2)[CH:23]=[CH:24][CH:25]=1)#[N:19]

Participants

9

Reactant 4

HCID 10340Sodium CarbonateHCID 67184N-bromobutanimideHCID 27343253-Cyanophenylboronic acidHCID 22613894HCID 22613894, compound

Product 1

HCID 22613898HCID 22613898, compoundYield 99.5%

Reagents, catalysts & solvents 4

HCID 178418397HCID 178418397, compoundCatalystHCID 887MethanolSolventHCID 1140TolueneSolventHCID 5943Carbon TetrachlorideSolvent

Procedure

A solution of 7.0 g of 3-bromo-5-methylphenol and 5.97 g of methyl bromoacetate and also 13 g of caesium carbonate in 100 ml of acetonitrile is stirred overnight at room temperature. After customary working up, 9.70 g of methyl 3-bromo-5-methylphenoxyacetate (“AB”) are obtained. A suspension of 2.0 g of “AB”, 100 mg of tetrakis(triphenylphosphine)palladium and 0.85 g of sodium carbonate in 50 ml of toluene is heated to boiling. A solution of 2.94 g of 3-cyanophenylboronic acid in 30 ml of methanol is then added dropwise and the mixture is heated under reflux for 14 hours. It is worked up in the customary manner and 2.17 g of methyl 3′-cyano-5-methylbiphenyl-3-yloxyacetate (“AC”) are obtained. A solution of 1.2 g of “AC” and 0.765 g of NBS in 50 ml of carbon tetrachloride is irradiated with UV light at room temperature. After customary working up, 1.54 g of methyl 3′-cyano-5-bromomethylbiphenyl-3-yloxyacetate (“AD”) are obtained. A solution of 185 mg of “AD”, 63.1 mg of 4-hydroxybenzonitrile and 172.7 mg of caesium carbonate in 10 ml of acetonitrile is stirred at room temperature for 4 days. After customary working up, methyl 3′-cyano-5-(4-cyanophenoxymethyl)biphenyl-3-yloxyacetate (“AE”) is obtained. A solution of 60 mg of “AE”, 69.5 mg of hydroxylammonium chloride and 101 mg of triethylamine in 10 ml of methanol is heated under reflux for 14 hours. After removal of the solvent, the residue is taken up in water. The solid is separated off and 70 mg of methyl 3′-N-hydroxyamidino-5-(4-N-hydroxyamidinophenoxymethyl)biphenyl-3-yloxyacetate (“AF”) are obtained. By reduction with H2/Raney nickel, methyl 3′-amidino-5-(4-amidinophenoxymethyl)biphenyl-3-yloxyacetate, FAB 433

Workup

  1. temperatureis heated to boiling
  2. temperaturethe mixture is heated
  3. temperatureunder reflux for 14 hours
  4. customare obtained

Sources & evidence

ORD record
ord-695b3f2c6f6d4f278c2174b749b1dd17
Source dataset
uspto-grants-2002_04
Patent number
US06380430B1

Reaction notes

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